Mass and heat transfer in catalytic reactions

Lucio Forni
1
Dipartimento di Chimica Fisica ed Elettrochimica, Universita di Milano, Via C. Golgi, 19 I-20133 Milan, Italy
Abstract
When a porous solid catalyst is added to a uid reactant, the reaction process becomes immediately much more complex
with respect to the homogeneous single-phase process. Indeed, since the reaction now takes place essentially at the surface of
the porous solid, diffusional heat and mass transfer intrusions may intervene. Then the kinetic analysis of heterogeneous
catalytic reactions cannot neglect the effect of such intrusions, since the rate of the reaction now corresponds to the slowest
step of the overall catalytic process, the so-called rate-determining step, and the heat and mass transfer intrusions may affect
considerably the relative rate of such steps. # 1999 Elsevier Science B.V. All rights reserved.
Keywords: Catalyst; Mass transfer; Heat transfer
1. Introduction
In reactions catalysed by porous solids the mole-
cules of the uid reactant may come in contact with
the active sites of the catalyst only by diffusing rst
through the uid layer, surrounding the catalyst par-
ticle (external diffusion), and then through the pore
network within the particle (internal diffusion). Since
the internal surface is usually by far larger than the
external one, the overall reaction rate can be strongly
affected by the ability of reactant in attaining the
active sites, i.e. by the rate of diffusion.
Furthermore, porous solid catalysts are usually
made of poorly heat-conductive materials. Hence,
for relatively highly exothermal or endothermal reac-
tions, a considerable temperature gradient may be
found along the particle radius. As a consequence,
since heat and mass transfer coefcients and mainly
the reaction rate constant depend on temperature,
different reaction conditions may be found along
the particle radius, so affecting considerably the
kinetics of the overall process.
2. Mass and heat transfer from the reacting fluid
to porous particles
The rate N (mol cm
2
s
1
) of mass transfer of a
given reacting species from a uid owing through a
bed of porous particles to the external surface of the
latter is given by
N = k
c
(c
0
c
s
). (1)
Incase of a gaseous reactant, Eq. (1) canbewrittenas
N = k
g
(p
0
p
s
). (2)
c (mol cm
3
) and p (Pa=N m
2
) being the concentra-
tion and the partial pressure of the reactant and the
subscripts 0 and s representing the bulk uid phase
Catalysis Today 52 (1999) 147152
1
Tel.: +39-02-266-03-289; fax: +39-02-706-38-129
E-mail address: forn@rs6.csrsrc.mi.cnr.it (L. Forni)
0920-5861/99/$ see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0 9 2 0 - 5 8 6 1 ( 9 9 ) 0 0 0 7 2 - 3
andtheexternal surfaceof theparticle, respectively. The
relationship between the two mass transfer coefcients
(k
c
and k
g
) is
k
g
=
k
c
RT
. (3)
The value of k
c
and k
g
can be calculated by means of
correlations, determined experimentally [1], between
the Sherwood (Sh = k
c
D
p
,D), Schmidt (Sc = j,, D)
andReynolds(Re = D
p
, u
s
,j) numbers, D
p
(cm) being
the catalyst particle diameter, D(cm
2
s
1
) the diffusion
coefcient of the reactant, , (g cm
3
) and j (Pa s) the
density and viscosity of the uid and u
s
(cm s
1
) the
supercial ow rate of the uid, referred to the overall
cross section of the catalyst bed, calculated in the
absence of catalyst.
The correlations are of the form
j
D
=
Sh
Re Sc
1,3
= f (Re). (4)
More explicitly we have
j
D
=
k
c
u
s
j
, D
_ _
0.67
=
k
g
P
u
s
c
j
, D
_ _
0.67
=
k
g
P
G
ms
j
, D
_ _
0.67
.
(5)
where P (Pa) is the total pressure and G
ms
=u
s
c the
molar supercial ow rate (mol cm
2
s
1
) of the
reactant.
As for heat transfer, through a similar reasoning
involving the Nusselt (Nu = h D
p
,k), Prandtl
(Pr = c
p
j,k) and Reynolds numbers, we have
j
H
=
h
c
p
, u
s
c
p
j
k
_ _
0.67
. (6)
where h (J s
1
cm
2
K
1
), c
p
(J g
1
K
1
) and k (J s
1
cm
1
K
1
) are the laminar coefcient for the uid
solid heat transfer, the heat capacity and the thermal
conductivity of the reacting uid, respectively.
The previously mentioned experimental relation-
ships are the following:
v for gaseous reactants, 3<Re<2000 and
0.416<c<0.788
j
D
c = 0.357 Re
0.359
. (7)
v for liquid reactants, 55<Re<1500 and 0.35<c<0.75
j
D
c = 0.25 Re
0.31
. (8)
v for liquid reactants and 0.0016<Re<55
j
D
c = 1.09 Re
0.67
. (9)
where c is the interparticle void fraction of the bed of
particles.
Finally, the relationship between j
D
and j
H
is
j
H
1.08 j
D
. (10)
3. Mass transfer within porous particles
Three diffusion modes can be observed, depending
on the catalyst pore size. When the pore diameter d
p
is
much larger than the mean free path ` of diffusing
molecules, the diffusion takes place in the usual
(Maxwellian) way, as observed outside the pores (bulk
or molecular diffusion). When d
p
` the diffusing
molecules hit upon the pore walls more frequently
than upon other molecules (Knudsen diffusion). In
microporous solids, such as zeolites, the pore diameter
of which is close to the size of the reactants' molecule,
the latter can diffuse within the pores only by remain-
ing constantly in contact with the pore walls (surface
or congurational diffusion).
It is generally accepted [2] that surface diffusion
can affect considerably the overall reaction rate only
for low-temperature processes. At high temperature a
total pressure difference across the pore is usually
present, generating a forced ow in pores.
The internal diffusion rate N
i
(mol cm
2
s
1
) can be
described by Fick's law (N
i
=D
e
(0c/0z), z being the
diffusion coordinate), in which an effective diffusion
coefcient D
e
(cm
2
s
1
) is inserted, given by
1
D
e
=
1
D
b.e

1
D
k.e
. (11)
where D
b,e
and D
k,e
are the effective diffusion coef-
cients for bulk and Knudsen diffusion, respectively.
They can be calculated by the following equations [1]:
D
b.e
=
D
b
0
t
. (12)
D
k.e
= 1.94 10
4
0
2
t S
g
,
p

T
M
_
. (13)
where D
b
(cm
2
s
1
) is the bulk diffusion coefcient, 0
the internal void fraction of the solid particle, t the
148 L. Forni / Catalysis Today 52 (1999) 147152
tortuosity factor of the pores, S
g
(cm
2
g
1
) the specic
surface area of the catalyst, ,
p
(g cm
3
) the particle
density, T (K) the reaction temperature and M
(g mol
1
) the molecular mass of the diffusing species.
In the absence of specic experimental data, a value of
ca. 0.5 and of ca. 4 can be attributed to 0 and t,
respectively [3].
For a spherical particle of radius r
1
(cm) (Fig. 1) the
prole of reactant concentration as a function of
particle radius may be calculated by means of a mass
balance referred to a spherical shell of thickness dr and
radius r. Putting c and c(dc/dr) dr the concentration
of the reactant at r=r and r=rdr, respectively,
we have
4 (r dr)
2
d
dr
c
dc
dr
dr
_ _
D
e
4 r
2
dc
dr
D
e
= r
a
4 r
2
dr. (14)
For a rst-order chemical reaction, the reaction rate
r
a
(mol cm
3
s
1
), referred to the unit volume of
catalyst particle, is given by
r
a
= k
s
S
v
c. (15)
k
s
(cm s
1
) being the reaction rate constant and S
v
(cm
2
cm
3
) the surface area per unit particle volume.
Developing Eq. (14) and neglecting the higher-order
innitesimals, we have
D
e
d
2
c
dr
2

2
r
dc
dr
_ _
= k
s
S
v
c. (16)
the integration of which allows one to obtain the
reactant concentration prole within the particle.
The integration can be made easier by introducing
a dimensionless parameter 1, known as Thiele
modulus
1 = r
1

k
s
S
v
c
i1
s
D
e

. (17)
where c
s
is the reactants' concentration at the external
particle surface and i the reaction order. 1 represents
the ratio of reactivity over diffusivity of the reacting
species and, for rst-order reactions, 1 is independent
of reactants' concentration.
The result of the integration is
c =
c
s
r
1
r sin h 1
sin h
r 1
r
1
_ _
. (18)
The prole is shown in Fig. 2, together with the
drop in concentration within the uid lm surrounding
the particle, according to the boundary-layer theory
[4].
4. Catalyst effectiveness
Under steady-state conditions and in the absence of
reverse reaction, the rate of reaction (mol s
1
) of a
reactant A equals the rate of diffusion of A from the
bulk uid to the external surface of the catalyst
particle. For a spherical particle we have
4
3
r
3
1
r
a
= 4 r
2
1
N
A
= 4 r
2
1
D
e
dc
dr
_ _
r=r
1
. (19)
Fig. 1. Scheme of a spherical catalyst particle.
Fig. 2. Concentration profile of reactant close to the external
surface and within a spherical catalyst particle. First-order reaction
kinetics.
L. Forni / Catalysis Today 52 (1999) 147152 149
Combining with Eq. (18) and solving
4
3
r
3
1
r
a
= 4 r
2
1
D
e
c
s
1
r
1
1
T g h 1

1
1
_ _ _ _
. (20)
In the absence of any diffusional resistance, i.e. if
the overall surface of the catalyst were exposed uni-
formly to the concentration c
s
of reactant, existing at
the external surface of the particle, the rate of con-
sumption of A would be
4
3
r
3
1
r
a
=
4
3
r
3
1
c
s
k
s
S
v
. (21)
The effectiveness or effectiveness factor j of the
catalyst is then dened by the ratio of Eq. (20) over
Eq. (21)
j =
3 D
e
1
r
2
1
k
s
S
v
1
Tgh 1

1
1
_ _
. (22)
Remembering the denition of 1 (Eq. (17)), we
have
j =
3
1
1
Tgh 1

1
1
_ _
. (23)
The dependence of j on 1 is shown in Fig. 3.
5. Non-isothermal catalyst particles
For a spherical particle and under steady-state
reaction conditions, the heat released or absorbed
by the reaction may be calculated by means of a heat
balance similar to the previously discussed mass
balance, referred to the same spherical shell (Fig. 1)
4
3
(r dr)
2
k
T
d
dr
T
dT
dr
dr
_ _
4 r
2
k
T
dT
dr
= 4 r
2
dr r
a
(H). (24)
Developing Eq. (24) and neglecting the higher-
order innitesimals, we get
k
T
d
2
T
dr
2

2
r
dT
dr
_ _
= r
a
(H). (25)
k
T
(J s
1
cm
1
K
1
) and H (J mol
1
) being the
thermal conductivity of the solid and the enthalpy
change connected with the reaction, respectively. The
temperature change within the particle may be calcu-
lated by integrating simultaneously Eqs. (16) and (25)
and by expressing the dependence on temperature of
the reaction rate constant k
s
by means of the Arrhenius
equation
k
s
= Ae
E
a
,RT
. (26)
A (cm s
1
) and E
a
(J mol
1
) being the so-called pre-
exponential factor and the apparent activation energy
of the reaction, respectively.
Two dimensionless parameters can be introduced to
classify the kinetic data of a given reaction in terms of
E
a
, H, and k
T
. Such parameters are the Prater number
u =
c
s
(H)D
e
k
T
T
s
=
T
max
T
s
T
s
. (27)
and the Arrhenius number
=
E
a
RT
s
. (28)
where T
s
is the temperature at the external surface and
T
max
the maximum temperature detected along the
radius of the particle.
It may be noticed that u=0, u<0 and u>0 for
isothermal, endothermal and exothermal reactions,
respectively. As for , a common value for most
catalytic reactions is =20, corresponding to
E
a
=100 kJ mol
1
and reaction temperature of ca.
600 K. The result of the integration is usually reported
as a set of curves of j versus 1 (Fig. 4). Similar sets of
curves can be calculated for different reaction orders
and catalyst particles of different shape [1,2]. It may
be observed that for exothermal reactions (u>0) j can
become higher than unity. Indeed, in this case the
effect of decreasing of reactants' concentration within
the particle is more than counterbalanced by the effect
Fig. 3. Effectiveness of a catalyst as a function of Thiele modulus
1. Spherical particles, first-order reaction.
150 L. Forni / Catalysis Today 52 (1999) 147152
of increasing temperature on the kinetic constant of
the reaction. Furthermore, it may be noted that for
highly exothermal reactions and 1<1, up to three
values of j may correspond to a given set of values
of 1, u and . Every one of these values of j represents
a steady state, in which the heat generated by the
reaction equals the heat carried away by the refriger-
ating system. Only the upper and lower situations
however represent an autostabilising state, the inter-
mediate one being intrinsically unstable. For a
detailed discussion of these aspects see e.g. [5,6].
6. Simultaneous effect of external and internal
diffusion on the kinetics of heterogeneous
catalytic reactions
For a catalyst particle immersed in a owing gas in
which a reactant A is present, the rate r
ed
of external
diffusion and the rate r
r
of reaction of A in the
presence of internal diffusion effects may be
expressed in terms of partial pressure of A (p
A
).
For a rst-order kinetics we have
r
ed
= k
g
a(p
A
p
As
). (29)
r
r
= j k
r
p
As
. (30)
where the subscript s refers to the external surface of
the particle, k
g
is the mass transfer coefcient of A, a
(cm
2
cm
3
) the specic surface area of catalyst and k
r
the reaction rate constant. r
ed
, r
r
, a and k
r
are referred
to unit volume of bed.
Under steady-state conditions r
ed
=r
r
, so that, by
combining Eqs. (29) and (30), the overall reaction rate
r
t
of the process can be written as
r
t
=
j k
r
p
A
1 (j k
r
,k
g
a)
=
j k
r
p
A
1 j Da
. (31)
Da=k
r
/k
g
a being the Damkohler number, expressing
the ratio of the rate of chemical reaction over the rate
of external diffusion of the reactant.
The following signicant cases may then occur:
1. When 1<1, and therefore j1, i.e. when internal
diffusion has no signicant effect, Eq. (31)
becomes
r
t

k
r
p
A
1 (k
r
,k
g
a)
=
k
r
p
A
1 Da
. (32)
But k
g
and k
r
depend on temperature as shown
in Fig. 5. Hence, for low temperature (T<600 K)
k
g
ak
r
, so that
r
t
k
r
p
A
. (33)
This means that the rate of the overall catalytic
process is governed by the chemical reaction
(chemical regime). On the other hand, at high
temperature k
r
k
g
a, so that
r
t
k
g
a p
A
. (34)
i.e. the overall rate is governed by the external
diffusion (external diffusional regime).
2. When 1>3, so that j3/1, Eq. (31), by recalling
the definition of the Thiele modulus (Eq. (17))
becomes
r
t
=
p
A
a

k
r
D
e
_
(r
1
a,3) (

k
r
D
e
_
,k
g
)
. (35)
Fig. 4. Effectiveness factor j versus Thiele modulus 1 =
r
1

k
s
S
v
,D
e
_
. u = c
s
(H)D
e
,k
T
T
s
), = E
a
,RT
s
= 20. First-
order reaction over spherical catalyst particles.
L. Forni / Catalysis Today 52 (1999) 147152 151
However, if the value of the effective diffusion
coefficient D
e
is low, so to have

k
r
D
e
_
,k
g
r
1
a,3, Eq. (35) becomes
r
t
=

k
r
D
e
_
p
A
3
r
1
. (36)
i.e. the overall rate is governed by internal diffusion
(internal diffusional regime).
Analogous considerations lead to similar, though
more complex, expressions in case of chemical reac-
tion of higher reaction orders [1].
References
[1] C.N. Satterfield, Mass Transfer in Heterogeneous Catalysis,
MIT Press, Cambridge, MA, 1970.
[2] J.M. Thomas, W.J. Thomas, Principles and Practice of
Heterogeneous Catalysis, VCH, Weinheim, 1997.
[3] J.T. Richardson, Principles of Catalyst Development, Plenum
Press, New York, 1989.
[4] L. Forni, Fenomeni di Trasporto, Cortina, Milano, 1994.
[5] S. Carra, L. Forni, Aspetti Cinetici della Teoria del Reattore
Chimico, Tamburini, Milano, 1974.
[6] J.J. Carberry, Chemical and Catalytic Reaction Engineering,
McGraw-Hill, New York, 1976.
Fig. 5. Dependence on temperature of k
r
= Ae
Ea,RT
and k
g
T
2
.
152 L. Forni / Catalysis Today 52 (1999) 147152